Sulfamethoxazole sorption by sediment fractions in comparison to pyrene and bisphenol A

The environmental behavior of antibiotics has attracted great research attention. However, their sorption mechanisms in soils/sediments are still unknown. Comparison of the sorption properties between the widely-studied hydrophobic organic contaminants (HOCs) and antibiotics may provide valuable insight to antibiotic sorption mechanisms. Thus, in this study batch experiments for pyrene (PYR), bisphenol A (BPA), and sulfamethoxazole (SMX) sorption were conducted on a sediment sample and its separated fractions. Our results showed the high sorption of PYR on black carbon and organic matter. Although high sorption of SMX was observed for both separated organic fractions (humic acids) and inorganic mineral particles, the original sediment particles showed relatively low sorption. Competitive sorption between SMX and dissolved humic acid on mineral particles was observed in this study. This competitive interaction is a unique process for antibiotic sorption in soils/sediments compared with apolar HOCs and may be one of the important factors controlling the antibiotic sorption.     

十六烷基三甲基溴化铵对重油在海洋沉积物上吸附的影响

研究了阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对重油在海洋沉积物上吸附的影响。结果表明,在CTAB初始质量浓度为0～20mg/L时,海洋沉积物对重油的吸附动力学过程符合伪二级吸附动力学方程,伪二级吸附速率常数随CTAB初始浓度增加、温度的升高而增大;吸附等温线符合Freundlich方程。随着CTAB初始浓度和盐度的增加、温度的降低,重油在海洋沉积物上的吸附量增大。标准吸附焓变(ΔH0)、标准吉布斯自由能变(ΔG0)、标准吸附熵变(ΔS0)的计算结果表明,重油在海洋沉积物上的吸附为物理吸附,是一个自发、放热、熵减小的过程。     

Influence of metal ion on sorption of p-nitrophenol onto sediment in the presence of cetylpyridinium chloride

Heavy metals and surfactants have a significant effect on the sorption of organic contaminants. In this study, batch equilibrium experiments were carried out to investigate the influence of Pb(NO(3))(2) on the sorption of p-nitrophenol (PNP) onto sediments in the presence of cationic surfactant cetylpyridinium chloride (CPC). Results indicated that in the complex system containing PNP, Pb(NO(3))(2) and CPC, the sorption of PNP decreased with increasing concentration of Pb(NO(3))(2) due primarily to competing for adsorption sites. Likewise, partitioning of PNP in adsorbed surfactant layers and micelles decreased with increasing level of Pb(NO(3))(2). Moreover, the influence of different metal ions (Pb(2+), Cd(2+), Zn(2+)) was examined and results indicated that the presence of heavy metals inhibited the sorption of PNP in the order: Pb(2+)>Cd(2+)>Zn(2+). The competitive effect of the heavy metals was in agreement with the hydration energy and hydrated radius. The results are believed to provide a useful insight into describing the transport and fate of PNP in natural environments.     

底泥性质对重金属生物淋滤效果的影响

生物淋滤技术是一项可以将重金属从污染底泥或土壤中分离出来的环境修复技术,具有反应温和、耗酸少、运行成本较低、去除效率高,以及脱毒后底泥的脱水性能好等优点。然而,底泥成分复杂、流域特异性高,这使得相似的生物淋滤工艺对不同底泥的重金属去除效果不尽相同、淋滤技术的工艺参数标准化难度增加。综述了底泥性质对淋滤反应的3方面影响:底泥中的有机质与酸可挥发性硫化物(AVS)会改变重金属的形态;pH、可还原性硫、水溶性有机物(DOM)会对淋滤功能菌的活性产生影响;底泥粒度和耗酸能力(ACC)也会影响重金属的化学淋出效果。在此基础上提出今后该技术有待开展的研究内容,以期为该技术的进一步推广应用提供理论依据和技术支撑。     

A field study on phytoremediation of dredged sediment contaminated by heavy metals and nutrients: the impacts of sediment aeration

Compared to traditional chemical or physical treatments, phytoremediation has proved to be a cost-effective and environmentally sound alternative for remediation of contaminated dredged sediment. A field study was conducted in a sediment disposal site predominantly colonized by Typha angustifolia under different sediment moisture conditions to estimate the phytoremediation effects of dredged sediment. The moisture content was 37.30 % and 48.27 % in aerated and waterlogged sediment, respectively. Total nitrogen (TN) content was higher in the waterlogged sediment than in the aerated sediment. The total Cd contents were lower in aerated sediment, which was mainly resulted from the lower exchangeable fraction of Cd. The bioaccumulation of P, Cu and Pb in T. angustifolia was promoted by waterlogging, and the belowground tissue concentrations and accumulation factors (AFs) of Cu were higher than that of other metals, which can be explained by that Cu is an essential micronutrient for plants. Consistent with many previous studies, T. angustifolia showed higher metal levels in roots than in above-ground tissues at both the sediment conditions. Due to the improved biomass produced in the aerated sediment, the removals of nutrients and the metals by plant harvest were higher from aerated sediment than from waterlogged sediment. It was indicated that maintaining the dredged sediment aerated can avoid release risk and plant uptake of metals, while the opposite management option can promote phytoextraction of these contaminants.     

ES稳定重金属污染底泥效果

就新型有机重金属稳定剂ES和常用稳定剂氧化钙、硫化钠、硫酸亚铁、磷酸氢二钠、壳聚糖对Cu、As、Cd、Hg单一重金属模拟底泥的稳定化效果进行了对比实验研究。结果表明,氧化钙对几种重金属均有一定稳定效果,但用量大,成本高;硫化钠也对4种重金属有一定效果,对Hg、Cu效果较佳,As、Cd效果一般;磷酸氢二钠则对Hg、As基本无稳定效果;硫酸亚铁虽对As有较高的稳定化率,对于其余3种重金属则基本无效;壳聚糖则对As有明显反作用。根据稳定模拟底泥实验结果对新型有机重金属稳定剂-ES的稳定现场原状污染底泥的工程应用和机理进行了研究。结果表明,投加量为5%,pH为8,液固比为1.2: 1时,ES对复合重金属底泥中的重金属稳定化率最高。经ES稳定后各重金属形态残渣态占较大比例,稳定性佳。     

微生物沥浸法去除底泥中的重金属

以硫酸亚铁盐为底物,培养以氧化亚铁硫杆菌为主要菌种的土著沥滤微生物,采用批式方法对湘江长沙段底泥进行微生物沥浸实验。实验结果表明,底物投加量与底泥固体浓度比(Sd/Sc)为1.5时已能满足底泥的微生物沥浸要求,进一步研究发现底泥固体浓度为13%、底物投加量为19.5 g/L、沥浸时间为6 d时,底泥中超标重金属Cd、Zn和Cu的去除率可分别达到83.1%、75.3%和61.2%;沥浸后底泥中大部分重金属以残渣态存在,且含量低于农用污泥中污染物控制标准,其中硫化物有机结合态Cu浸出较Zn、Cd需更低的pH,且Cu以间接机理浸出为主;以Fe2+为底物的沥浸体系中,黄铁矾的重吸附或共沉淀是沥浸实验后期重金属浸出率下降的原因之一。     

表面活性剂对Cd2+在沉积物上吸附行为的影响

以Cd2+为重金属代表,阴离子表面活性剂十二烷基苯磺酸钠(SDBS)、阳离子表面活性剂氯化十六烷基吡啶(CPC)、非离子表面活性剂辛基酚聚氧乙烯醚(TX-100)为表面活性剂代表,用实验模拟法研究了3种类型的表面活性剂对Cd2+在沉积物上吸附行为的影响.结果表明,不同种类的表面活性剂对Cd2+在沉积物上的吸附影响不同,SDBS对Cd2+的吸附影响可分为2个阶段,当SDBS初始质量浓度从0 mg/L增加到2 600 mg/L,Cd2+的吸附量从1.52 mg/g增至1.88 mg/g,增加了23.7%,随着SDBS初始浓度继续增加,Cd2+的吸附量开始下降,当SDBS初始质量浓度增至16 000 mg/L,Cd2+的吸附量降低至0.34 mg/g;CPC主要通过在溶液中电离出CP+,CP+与Cd2+竞争沉积物表面的吸附位从而抑制Cd2+的吸附,当CPC初始质量浓度从0 mg/L增加至16 000 mg/L,Cd2+的吸附量从1.50 mg/g降低至0.52 mg/g;TX-100能轻微抑制Cd2+在沉积物上的吸附,当TX-100初始质量浓度从0 mg/L增加到16 000 mg/L时,Cd2+吸附量从1.52 mg/g减少至1.35 mg/g.     

河流重金属污染底泥的稳定化实验研究

以实现河道疏浚底泥中富含的重金属Cu、Zn、Ni的稳定化为目标,选用EDTA、DTCR、Na2S、Na2S2O3、膨润土、水泥及自主研发的特殊胶凝材料作为稳定剂,对底泥中的重金属进行固化稳定,通过分析稳定后重金属浸出液浓度及赋存形态变化,探讨各药剂稳定效果,并寻求稳定剂的最佳投加量.研究表明,7种稳定剂对3种重金属的综合稳定化效果由好到差依次为:水泥> 胶凝材料> 膨润土> DTCR> 硫化钠> 硫代硫酸钠> EDTA;对Cu、Zn、Ni单种重金属而言,稳定效果最好的药剂分别为膨润土、胶凝材料及DTCR,而EDTA则使重金属浸出液浓度升高.除EDTA外,其他药剂对重金属Cu和Zn的稳定效果要明显优于Ni.根据稳定后重金属赋存形态变化结果,EDTA可使重金属可交换态比例升高,而膨润土对重金属4种形态分布基本无影响,其他药剂使重金属可交换态比例降低.     

硫酸盐对电子垃圾拆解地底泥中重金属形态的影响

为研究硫酸盐对重金属形态分布的影响规律,评价不同条件下的重金属生态风险,采集广东清远某电子垃圾拆解区附近河流底泥,通过投加不同浓度硫酸盐,采用BCR四步提取法分析厌氧培养28 d期间铜、铅、锌、镉的形态变化。结果表明：灭菌条件下,重金属的形态基本保持不变;在空白条件下Cu、Pb、Zn和Cd 4种重金属由不稳定态向稳定态转化,其转化率分别是7%、5%、11%和5%,锌的变化最明显;与空白相比,硫酸盐的投加会加大这4种重金属的转化,其影响顺序为：Cu > Cd > Zn > Pb。硫酸盐的投加可促进硫酸盐还原菌的生长,当硫酸盐浓度在286~655 mg·kg-1范围时,硫酸盐还原菌的数量随着硫酸盐浓度升高而增加。实验运行到后期,高浓度的H2S会对硫酸盐还原菌产生毒害作用,因此重金属的形态并不会一直向稳定态转化,研究结果表明,高浓度硫酸盐条件可降低重金属的迁移能力,有利于重金属污染场地的修复。     

液固比对含重金属水泥熟料制品中重金属释放的影响

通过模拟煅烧试验制取水泥熟料,参照JGJ 55-2000（《普通混凝土配比设计规程》）制取混凝土样品,参考SR003.1和NEN 7375浸出试验,分别研究液固比对粒状及块状混凝土样品中重金属（Cr、Ni和As）释放的影响。结果表明,在不同液固比条件下粒状混凝土中的重金属浸出浓度为Cr>Ni>As,Cr、As浸出浓度基本保持不变,分别为2 500 μg/L左右和5～6 μg/L,Ni在液固比（L∶S）<6时,浸出浓度随着液固比的增加而降低,在L∶S>6时,浸出浓度较稳定,为35.7～41.5 μg/L;浸出量均随着液固比的增加而增大。液固比（L∶S）<10时,块状混凝土中重金属累积释放量及扩散系数均随液固比的增加而增大,当L∶S>10时两者基本保持不变。     

The removal of heavy metals in urban runoff by sorption on mulch

A series of adsorption experiments was conducted in order to assess the ability of three mulches to remove several of the heavy metal ions typically encountered in urban runoff. Three types of mulch, cypress bark (C), hardwood bark (H), and pine bark nugget (P), were selected as potential sorbents to capture heavy metals in urban runoff. The hardwood bark (H) mulch had the best physicochemical properties for adsorption of heavy metal ions. In addition, because of its fast removal rate and acceptably high capacity for all the heavy metal ions, it was concluded that the H mulch is the best of the three adsorbents for treatment of urban runoff containing trace amounts of heavy metals. In order to investigate the sorption isotherm, two equilibrium models, the Freundlich and Langmuir isotherms, were analyzed. The sorption of these metals on H mulch conformed to the linear form of the Langmuir adsorption equation. At pH 5 and 6, the Langmuir constants (S(m)) for each metal were found to be 0.324 and 0.359 mmol/g (Cu); 0.306 and 0.350 mmol/g (Pb); and 0.185 and 0.187 mmol/g (Zn) at 25 degrees C.     

不同浸提剂对污染河道底泥中重金属的浸出影响

以某有色金属冶炼企业排放口下游河道底泥为研究对象,分别采用无机酸(盐酸、硫酸、硝酸)和有机酸(醋酸、柠檬酸、苹果酸和丁二酸)研究在不同酸性条件(pH为2~6)下Pb、Cd、Zn、Cu的浸出效果。结果表明,有机酸的浸提能力明显高于无机酸,且4种重金属的浸出浓度均随着pH的升高而迅速降低。对无机酸而言,当pH3时,重金属的浸出浓度趋于稳定;对有机酸而言,在pH为2~5的较大范围内,醋酸表现出较高的浸提能力,而柠檬酸对Pb和Cu没有明显的浸出效果。结合泥质特点,从重金属的络合、沉淀、水解、吸附等反应过程对其浸出特征进行了分析,同时提出醋酸良好的缓冲能力是其浸提效果优于其他有机酸的重要原因。     

Phosphorus sorption on marine carbonate sediment: phosphonate as model organic compounds

Organophosphonate, characterized by the presence of a stable, covalent, carbon to phosphorus (C-P) bond, is a group of synthetic or biogenic organophosphorus compounds. The fate of these organic phosphorus compounds in the environment is not well studied. This study presents the first investigation on the sorption of phosphorus (P) in the presence of two model phosphonate compounds, 2-aminothylphosphonoic acid (2-AEP) and phosphonoformic acid (PFA), on marine carbonate sediments. In contrast to other organic P compounds, no significant inorganic phosphate exchange was observed in seawater. P was found to adsorb on the sediment only in the presence of PFA, not 2-AEP. This indicated that sorption of P from phosphonate on marine sediment was compound specific. Compared with inorganic phosphate sorption on the same sediments, P sorption from organic phosphorus is much less in the marine environment. Further study is needed to understand the potential role of the organophosphonate compounds in biogeochemical cycle of phosphorus in the environment.     

Predictions of binary sorption isotherms for the sorption of heavy metals by pine bark using single isotherm data

The adsorption of three heavy metal ions by pine bark was studied. The study was divided into two parts; single component adsorption of the metals Cu2+, Cd2+ and Ni2+ and bisolute adsorption of the three binary systems Cu2+-Cd2+, Cu2+-Ni2+ and Cd2+-Ni2+. Extended Langmuir model, extended Freundlich model. Sips model and ideal adsorption solution theory (IAST) models were used to predict the equilibrium uptake for Cu2+, Cd2+ and Ni2+ in the binary diluted solutions using the single adsorption constants. The experimental data of single isotherm adsorption process were found to follow Langmuir isotherm model with less accuracy than Freundlich and Sips models. Whereas, the predictions of bisolute adsorption isotherms of the mentioned three systems, Cu2+-Cd2+, Cu2+-Ni2+ and Cd2+-Ni2+, showed good agreement with experimental data when using Extended-Langmuir, Extended-Freundlich and IAST. However, the only good fit of the Sips model was with the Cu2+-Cd2+ system.     

Bioleaching of heavy metals from sediment: significance of pH

Bioleaching process, which causes acidification and solubilization of heavy metals, is one of the promising methods for removing heavy metals from contaminated sediments. The solubilization of heavy metals from contaminated sediments is governed by the sediment pH. In the present study, the significance of pH in bioleaching of heavy metals from contaminated sediment was evaluated at different solid contents of sediments in a bench-scale reactor. Results showed that a temporal change of pH in the bioleaching process was effected by the buffering capacity of the sediment particulates. The variations of pH in this bioleaching process were calculated by a modified logistic model. It was observed that solubilization of heavy metals from sediments is highly pH-dependent. In addition, a non-linear equation for metal solubilization relating pH value in the bioleaching process was established. This allows an easier and faster estimate of metal solubilization by measuring pH in the bioleaching process.     

电动联合法对复合重金属污染底泥的修复

河流与湖泊底泥中重金属污染物的清除是实现水体彻底净化及底泥工程利用的关键。以增加了电解液循环的电动联合装置为修复设备,以Cu、Zn、Pb、Cr、Ni污染底泥为研究对象,结合小试模拟和中试模拟实验,明确修复装置对复合污染底泥的净化修复效果,并优化污染物回收的技术参数。结果表明,增设电解液循环有助于增强复合污染底泥中重金属离子的迁出,在小试模拟和中试模型实验中,底泥污染物的去除率分别达到了74%~84%和52%~60%;中试模型实验修复后底泥中的Cr、Cu、Ni和Zn含量分别为140.31、314.47、250.93、464.17 mg·kg⁻¹,低于《土壤环境质量-建设用地土壤污染风险管控标准》(GB 36600-2018) 的筛选值。在两极电解液增设pH调节装置和斜板沉淀池有助于以Cr(OH)₃、Cu(OH)₂、Ni(OH)₂和Zn(OH)₂沉淀物的方式对重金属离子进行回收,阳极电解液pH控制在5.0~6.5,阴极电解液pH控制在10时,阴阳极两侧电解液中重金属沉淀回收率均达99%。增加了电解液循环的电动联合修复技术可同步实现底泥污染物的净化及回收。     

Influence of sediment acidification on the bioaccumulation of metals in Ruditapes philippinarum

Background, aim and scope

The influence of pH (range 6.5–8.5) on the uptake of Zn, Cd, Pb, Cu, Ni, Cr, Hg, and As by juveniles of the clam Ruditapes philippinarum was examined in order to understand whether variation in sediment pH has significant repercussions on metal bioaccumulation.

Materials and methods

Clams were exposed to sediments collected in three locations in the Gulf of Cadiz (Huelva, Guadalquivir and Bay of Cadiz) and to contaminated particles derived from an accidental mining spill in Spain.

Results

With a notable exception of metal Cd, the concentration of metals within clams significantly increased (p?<?0.1) when sediment pH was lowered by one or two units. Moreover, the magnitude of this effect was dependent on the type of sediment contamination.

Discussion

Lower pH increases metal solubility and reduces or invert the metal sorption of metals to sediments. Increases in free metal ions in water favors metal uptake by clams, hence pH is an important factor controlling the mobility of these metals within sediments and their subsequent bioaccumulation within biota. Although sediment-water exchange of Cd can increase with acidification, this excess may be counterbalanced by the presence of ligands in seawater preventing the uptake by organism. Besides chlorines, Cd has also an affinity with carbonates and other ligands present in sea water. These Cd-carbonate complexes may reduce the bioavailable to organisms.

Conclusions

These results highlight the potential implications of sediment acidification, either due to the storage excess of organic matter or to the forced capture of CO₂, on the increasing metal availability to benthic organisms.

Recommendations and perspectives

This kind of studies should be increased to address the influence of acidification in the behavior, bioavailability, toxicity, and risk assessment of contaminants associated with sediments either above sub-seabed geological formations in marine environments or in high enriched by organic matter in estuarine areas. Recently, the capture of CO₂ in marine environments has been approved and started; it is necessary to address the potential impacts associated with leakages or other events occurring during the procedure of injection and storage of CO2.     

Influence of heavy metals on the microbial degradation of diesel fuel

The degradation of diesel fuel by a microbial community from a soil polluted by heavy metals (h.m.) in the presence of Cu, Ni, Zn, Pb, Cd, Hg and Cr (as chromate) was investigated. Experiments were conducted with soil slurries and the extracted community in liquid cultivation. The concentrations applied were in the sub-mM and mM range. Whereas the slurries displayed no significant effect, degradation in liquid culture was increasingly inhibited by higher metal concentrations. The course of degradation in suspension was demonstrated by the oxygen consumption. The order of toxicity was found to be: Hg > Cr(VI) > Cu > Cd > Ni > Pb > Zn. The absence of any effect for slurries was due to the non-availability of the metals in the soil, and to precipitation or adsorption to the soil in the case of amendment. The paper also includes results on the availability of h.m. and changes to the community after exposure.     

Effects of heavy metals and nitroaromatic compounds on horseradish glutathione S-transferase and peroxidase

Glutathione S-transferase (GST) and peroxidase (POX) activities have a direct relation to the effect of stress on plant metabolism. Changes in the activities of the enzymes were therefore studied. Horseradish hairy roots were treated by selected bivalent ions of heavy metals (HMs) and nitroaromatic compounds (NACs). We have shown differences in GST activity when assayed with substrates 1-chloro-2,4-dinitrobenzene (CDNB) and 1,2-dichloro-4-nitrobenzene (DCNB). The conjugation of DCNB catalysed by GST was inhibited in all roots treated with HMs as compared to non-treated roots, whereas NACs caused induction of the activity in dependence on the exposition time and concentration of compounds. The conjugation of CDNB by GST was not affected to the same extent. The increase of GST activity was determined in cultures treated by nickel (0.1 mM) and diaminonitrotoluenes (DANTs, 0.1 mM) for 6 h, whereas the roots treated by 2,4,6-trinitrotoluene (TNT), 4-amino-2,6-dinitrotoluene (ADNT) and dinitrotoluene (DNT, 1.0 mM) needed 27 h treatment to induce the activity. The POX activity of cultures treated by HMs was inhibited to 17-35% in comparison to non-treated cultures. The POX activity of roots treated by TNT (0.1 and 1.0 mM) for 6 and 27 h and by ADNT (0.1 and 1.0 mM) for 6 h was inhibited. A partial increase of POX activity was measured in roots treated by all NACs for 27 h. The content of oxidized glutathione (GSSG) and reduced glutathione (GSH) in the roots differed significantly. It was followed as a symptom of the stress reaction of the plant metabolism to the effect of NACs and HMs.